JP6895974B2 - Addition manufacturing using reactive fluids and products made using this - Google Patents

Description

The present invention claims the priority of US Patent Provisional Application No. 62 / 271,901 filed on December 28, 2015, all of which are cited in the text. The present invention relates to methods, devices, and products manufactured by performing an additive manufacturing (AM) process, in particular, the addition of using an energy beam to selectively melt a material to produce an object. Regarding the manufacturing process. Furthermore, the present invention relates to methods and systems that actively manipulate the surface of a material using reactive fluids before and / or during the addition manufacturing process.

The additive manufacturing process (also referred to as laminated modeling), also called a 3D printer, is an already established but mature technology. In a broad sense, the additive manufacturing process relates to the manufacture of a 3D object, in which a continuous layer material is deposited to create a net shape or near net shape (NNS). Additive manufacturing includes a wide variety of manufacturing and prototyping techniques referred to by various known names, including freeform fabrication, 3D printers, rapid prototyping / tooling, and the like. Additional manufacturing technology can manufacture complex parts from a variety of materials.

Currently, a large number of additional manufacturing processes are available, and special additional manufacturing processes use energy beams (eg, electron beams) or electromagnetic radiation (eg, laser beams) to make materials (eg, powders, pillars). , Wire, or fluid) is sintered or melted to create a solid 3D object. Here, the particles of the powder material are combined. The most commonly used methods in combination with powder materials are electron-beam melting (EBM), selective laser melting (SLM) or direct metal laser sintering (DMLS), Selective laser sintering (SLS), Fused deposition modeling (FDM), fused filament fabrication (FFF), or powder bed and inkjet head 3D printing, 3DP). These powder layer processes are collectively referred to as laser powder deposition or laser additive manufacturing (LAM). Selective laser sintering is a prominent additional manufacturing process that uses a laser beam to sinter or melt fine powders to achieve high speed manufacturing of functional prototyping and tooling. More specifically, sintering causes the powder particles to fuse (agglomerating) at a temperature lower than the melting point of the powder material, except that melting completely melts the powder particles and solid homogeneous mass. ) Need to be formed. Specific processes of laser sintering or laser melting include a heat transfer step to the powder material and a subsequent sintering or melting step of the powder material. Laser sintering and melting processes are applied to a wide range of powder materials, but the scientific and technical aspects of the manufacturing process are not yet fully understood, for example, sintering or melting rates and laminate molding. The effect of processing parameters during the process on the evolution of microstructures is not well understood. This process involves various heat, mass, and momentum transport modes, and chemical reactions that occur on the powder surface and complicate the process.

Although various laser addition manufacturing formats offer high potential for the production and repair of complex objects, they are limited by some of the drawbacks present with the use of powdered materials. One of the drawbacks is the reactivity between the surface of the powder material and the elements in the air such as oxygen and nitrogen. When the powder material contains iron, aluminum, and titanium as reactive metals, the surfaces of these metal particles react with the gas and eventually have microstructural imperfections (eg, crevices, impurities, or inclusions) in the product. Is formed. Such shortcomings lead to disastrous failure. These impurities include metal oxides and metal nitrides, and their drawbacks are not limited to impurities, gaps, or inclusions, and their ratio increases as the surface area of the powder material increases.

In the past, unnecessary chemical reactions have been reduced by forming powdered materials in a hypoxic environment. However, the handling of hypoxic powder materials utilizing the inert gas environment, which is carried out from the time of manufacturing the powder material to the actual use of the powder material in the addition manufacturing process, is classified according to the manufacturing cost of the powder material and the size of the powder. , Transportation, and safety assurance costs are significantly increased. This is due to the high explosiveness of the hypoxic metal powder. When not treated in this way, unfortunately, the presence of oxides or other impurities on the surface of the powder material prevents the adhesion of the powder used in the manufacture of metal products, and the mechanical of the manufactured product. The characteristics have deteriorated. Many / large micropores and disordered grain arrangements are formed due to the temperature gradient during the process, and the grain structure with such micropores and grain arrangements is a residual stress in the manufactured product. Caused.

The powder material easily absorbs moisture, and in the case of metal powder, the moisture easily forms a metal oxide and causes unnecessary porosity in the metal object formed by the laser powder deposition. Moisture is also a source of hydrogen for high-strength steels, forming a source of hydrogen on the powder surface and in the products produced, which later leads to cracking and hydrogen embrittlement.

To further mitigate the harmful effects of air and moisture on the powder material, the molten pool created by laser powder deposition is protected by applying an inert gas such as argon or helium. However, such protection cannot remove pre-existing oxides that are likely to form on the outer surface of the material powder during manufacturing, storage and operation. As a result, these oxide-coated metal-filled materials need to be reduced during the melting process to avoid drawbacks such as porosity and metal deposition. In the post-deposition treatment, for example, hot isostatic pressing (HIP) is commonly used to sink micropores (gap), inclusions, and cracks, improving the properties of the laser deposited metal. In order to avoid absorption of moisture, a method of storing the metal powder filling material in a preheated storage tank is also commonly used. Such protection and post-treatment methods are also very important for metal powders containing highly reactive metals (eg, superalloys) and fine particle powders with large surface areas.

On the other hand, another technique to reduce the harmful effects of air is to use flux with the powder material to try to protect the molten pool created by laser powder deposition and remove impurities. (See, eg, US Patent Application No. 2013/0136868). It prevents the product produced by the flux from reacting with the gas in the air, for example, reacting with the shield gas or a mixture of gases discussed above. However, the flux is a solid material and is sometimes incorporated into the material of the manufactured product.

Pretreatment of raw powder materials used in some additive manufacturing processes is also often required. Pretreatment involves coating, degassing, and heating the powder. Degassing is used to remove water vapor in powder particles. When exposed to the environment, the powder surface oxidizes very quickly during the manufacturing process. Water vapor is absorbed into the oxide, creating voids in the material formed by the addition manufacturing process. Hydrogen is formed by the method of removing water from the produced material, further embrittlement of the final material. The above-mentioned method for removing water vapor from powder includes various degassing methods. For example, Chinese Patent Application No. 105593185A describes a method for producing hypoxic metal titanium powder using a hydrogen atmosphere and hydrogen embrittlement. However, safe transportation / operation is complicated in order to avoid reaction with oxygen because the hypoxic metal powder has high explosiveness.

Further, as a conventional method, a method of reducing a large amount of metal oxide by using hydrogen at a high temperature at which a reduction reaction can be sufficiently carried out after production using a metal oxide paste (for example, US Patent Application No. 2013). / 0136868 (see Gazette No. 0136868) also has a shortage. This is because it is difficult to reduce oxides in manufactured products because it is difficult for gas to enter and diffuse. High temperature heat treatment of the gas causes unwanted powder sintering.

In view of the above, understanding that there are some problems, drawbacks, or disadvantages regarding the technology of laser addition manufacturing, and improving the method and equipment for manufacturing the near-net shape object, the tolerance of the finished product And / or high quality surface treatment of the finished product and / or reduction or elimination of cracks, inclusions and micropores between sedimentation in the finished product. Can be understood. For this reason, a laser addition manufacturing system is required to achieve active manipulation of the surface of the material by introducing at least one reactive fluid or fluid mixture before and / or during the addition manufacturing process. Can be done. Reactive fluids or fluid mixtures react with the surface of the substrate, for example, but not limited to, powders, plasmas, columns, wires, fluids, etc. are deposited and different parts of the substrate are deposited. It can be formed to have different substrate properties. By controlling / improving / adjusting the surface of the substrate, the mechanical and / or chemical properties of the manufactured object can be enhanced by manipulating the surface properties of the substrate.

The methods and devices provided by the present invention apply to additive manufacturing techniques, where the reactive fluid is brought into contact with, for example, but not limited to, a powder, plasma, prism, wire, or fluid substrate. .. The reactive fluid adjusts the surface of the substrate before, during, or after the energy beam is applied to achieve the desired chemistry. The energy beam is used for selective sintering (fuse) or melting of the substrate to produce a 3D object.

Based on the first aspect of the invention, the chemical composition of the surface of the substrate is at least one reactive fluid or fluid mixture that chemically reacts with the surface of the substrate before, during, and / or after the addition manufacturing process. Can be controlled / improved / adjusted by introducing. Fluid mixtures, including gas mixtures, substitute / or mix pure purge gas such as helium, argon, or nitrogen in chamber bodies and in metal powder transport lines, metal powder transport vessels, or. Used in a used metal powder container. The gas mixture contained in the fluid mixture contains other gas components that chemically reduce hydrogen, carbon monoxide, or surface oxides and / or clean or remove impurities on the material surface of the solid powder.

The present invention comprises the treatment of a material with a gas or a plurality of gases, wherein the gas comprises a gas mixture and is used, for example, to recover and reuse used metal powders to reduce the cost of the powders. Can be done. Further, these gases having high thermal conductivity (for example, helium) are used as a smelting gas or a balance gas, and effectively reduce the residual stress due to the temperature gradient.

In the present invention, a gas containing a gas mixture is further used to remove hydrogen in the substrate or the product produced and / or intentionally oxidize the surface of the substrate. As mentioned above, it is known that hydrogen on the surface of the base material and in the produced product causes hydrogen embrittlement. Based on the present invention, _{a gas containing a gas mixture having CO, CO 2} and / or a fluorocarbon compound is used to remove hydrogen and enhance the mechanical strength of the produced product.

The present invention further considers that the use of a gas containing a gas mixture will result in the formation of nitrides, carbides, borides, phosphides, silices, or other chemical layers on the surface of the substrate, eg, , But not limited to, the wear resistance and corrosion resistance of products manufactured by metal powder are enhanced.

Any combination of these gases is used to simultaneously form binary, ternary, or even higher order compounds, such as nitrides and borides.

The present invention further considers that the gas / fluid containing the mixture is used to modify the alloy components of the substrate before, during, and / or after the addition production. Gases / fluids containing volatile organometallic components are used to introduce or deposit metals onto the surface of the powder by chemical vapor deposition, atomic layer deposition, or other processes, thus being used in 3D printer processes. To.

The present invention makes that the use of reactive fluids containing the mixture is ideally adapted to be used together in an independent laser cutting process or combined with an additional manufacturing process combined with a laser cutting process. Consider further. In this example, the present invention considers that the object to be manufactured is further molded using a laser, and the laser melts, burns, or vaporizes and cuts the substrate. After the cutting and / or during the period, the surface of the manufactured object is exposed to a reactive fluid and / or a mixture thereof so that the entire surface of the manufactured object also has the required chemistry. ..

The technical effect of the present invention is the ability to improve mechanical properties, for example, metal products manufactured by laser addition manufacturing have higher wear resistance, corrosion resistance, mechanical strength, and lower residual stress. It is hoped that it is not limited to any theory, and that the mechanical and / or chemical properties of the manufactured product depend on the chemical composition, the substrate of the manufactured product, the particle structure of the surface, and the substrate used in the process. It is considered. The presence of oxides or other impurities on the surface of the substrate prevents the adherence of the substrate of the manufactured product and reduces the mechanical properties of the manufactured product. Due to the temperature gradient during the process, residual stress is generated in the product where the grain structure with many / large micropores and irregular grain arrangement is manufactured.

Other embodiments and features will be clarified in the following description, and those who have conventional knowledge in the art can understand these embodiments and technical features to some extent after studying the present specification, or the embodiments described. You can learn by implementing. The features and favorable conditions of the embodiments described are understandable and achievable through the tools, combinations and methods described herein.

The features and advantages of the present invention can be further understood by reference to the rest of the specification and the drawings.

It is a schematic diagram which shows the addition manufacturing apparatus which covers one aspect of this invention, and a reactive fluid and a base material come into contact with each other in a build chamber. It is a schematic diagram which shows the addition manufacturing apparatus which covers one aspect of this invention, and a reactive fluid and a base material come into contact with each other before entering a build chamber. It is a schematic diagram which shows the addition manufacturing apparatus which covers one aspect of this invention, in which a reactive fluid and a substrate are stored in the same container and come into contact with each other before entering a build chamber.

In the schematic, similar members and / or features have the same reference numerals. In addition, many types of members having the same form are distinguished by using an underline or a second reference numeral. For example, when having only the first code in the specification, the description is valid only for similar members having the same first code and has nothing to do with the member having the second code.

The following definitions apply to the present invention. The additional manufacturing process (AM processes) (or referred to as laminated molding) is used below for the production of a useful 3D object and relates to any process including a step in which the shape of the object is formed one layer at a time. Additional manufacturing processes include electron-beam melting (EBM), selective laser melting (SLM) or direct metal laser sintering (DMLS), and direct metal laser melting (DMLS). melting, DMLM, selective laser sintering (SLS), fused deposition modeling (FDM), fused filament fabrication (FFF), powder bed and inkjet head 3D printing (powder) Includes bed and inkjet head 3D printing (3DP), laser net shape manufacturing, direct metal laser sintering (DMLS), plasma transferred arc, freeform fabrication, etc. Energy beams (eg, electron beams) or electromagnetic radiation (eg, laser beams) are used in certain types of additive manufacturing processes to sinter or melt the powder material. Relatively expensive materials are commonly used in additional manufacturing processes, such as, but not limited to, powders, metal powder materials, prisms, fluids, or wires.

For ease of understanding, the following describes metal powders, but considers the use of any material, eg, but not limited to, the use of powders, prisms, fluids, or wires, and thus with limited conditions. It should not be considered. The present invention relates to an additional manufacturing process, which is a method of manufacturing an object (object, member, part, product, etc.) at high speed, in which a plurality of thin unit layers are sequentially formed to produce the object. Further, a multi-layered metal powder is laid and an energy beam (for example, a laser beam) is irradiated, and the particles of the metal powder in each layer are sequentially sintered (fused) or melted (melted) to form the layer or substrate. Is cured. According to one aspect of the invention, at least one reactive fluid or fluid mixture that reacts with the surface of the metal powder or various powders is introduced into the metal powder before, during, and / or after the addition manufacturing process. Upon contact, the chemical properties of the surface of the powder material are actively manipulated. This controls / improves / adjusts the chemical composition of the surface of the powder material before, during, and / or after the addition manufacturing process. Chemical reduction of hydrogen, carbon monoxide, or other surface oxides and / or impurities on the solid powder surface in the absence or use of pure purification gases (eg, helium, argon, or nitrogen). A gas mixture containing a gas component that cleans or removes the gas is used in the build chamber itself and on the metal powder transport line, in the metal powder transport vessel, or in the used metal powder containment vessel.

The present invention includes bulk modification of the substrate, eg, an ultrathin film / layer (eg, 1 μm or less), exposed to a reactive fluid and supplemented with energy (eg, thermal diffusion during a semiconductor process). ) Allows adjustment of the overall nature.

The present invention comprises the treatment of a substrate with a plurality of gases including a gas or a gas mixture, and is used for recovering and reusing used metal powders, reducing the cost of the powders. Further, these gases having high thermal conductivity (for example, helium) are used as a smelting gas or a balance gas, and the residual stress due to the temperature gradient is effectively reduced.

The present invention further uses a gas containing a gas mixture to remove hydrogen in the powder or in the product produced and / or intentionally oxidize the surface of the powder. As mentioned above, it is known that hydrogen on the surface of the base material and in the produced product causes hydrogen embrittlement. According to the present invention, _{a gas containing a gas mixture having CO, CO 2} and / or a fluorocarbon compound is used to remove hydrogen and enhance the mechanical strength of the produced product. In addition to these gases, oxygen, ozone, and / or hydrogen peroxide can be used not only for removing hydrogen, but also for forming metal oxide materials.

The present invention uses a gas containing a gas mixture to form nitrides, carbides, borides, phosphides, silices, or other chemical layers on the surface of a substrate to provide wear resistance to the products produced. Further consideration is given to enhancing corrosion resistance. Any combination of these gases can be used to simultaneously form binary, ternary, or even higher order compounds, such as nitrides and borides. The present invention further considers that the gas / fluid containing the mixture is used to modify the alloying components of the powder material before and / or during the addition production. Gases / fluids containing volatile organometallic components are used to introduce or deposit metals onto the surface of the powder by chemical vapor deposition, atomic layer deposition, or other processes, thus being used in 3D printer processes.

For a detailed description of the laser sintering / melting technique, refer to U.S. Patent Applications Nos. 4,863,538, 5,017,753, 5,076,869, and 4,944,817. For this process, a laser beam is used to selectively melt the powder material by scanning the cross section of the material on the bed. These cross sections are scanned based on the desired 3D depiction of the object. The depiction is obtained from a variety of sources, such as CAD (computer aided design) files, scan data, or other sources.

In one embodiment, the addition process equipment includes a build chamber in which the article is manufactured, a mobile manufacturing platform located in and on which the article is manufactured, and a substrate / fluid. It is equipped with a transportation system and an energy transmission system. The substrate / fluid transport system transports the chemically adjusted substrate to the manufacturing platform. In a selective embodiment, the heating system is used to heat the substrate and the platform with heated gas. By matching the shape of the object, the substrate is only fed to some part of the movable platform on which the process is performed.

According to some aspects of the invention, the substrate is a metallic material, eg, but not limited to aluminum and its alloys, iron and its alloys, titanium and its alloys, nickel and its alloys, stainless steel, cobalt-chromium alloys, Includes tantalum and niobium. The reactive fluid is selected according to the particular metal material used and the desired surface chemistry. Reactive fluids include, for example, but not limited to highly diffusive gases and / or gas mixtures such as reductions, oxidants, reactive gases, or reactive fluids. Chemically reduce hydrogen, carbon monoxide, or surface oxides and / or clean impurities on the substrate surface in situations where a pure purification gas (eg, helium, argon, or nitrogen) is not used or used. The fluid of the gas mixture containing the other gas components to be removed is used on the build chamber itself and on the substrate transport line, in the substrate container, or in the used substrate container.

The method for producing a 3D structure includes a step of forming a substrate by depositing at least one of the above-mentioned substrates of the first layer on the platform. After at least the other layers of the substrate have been deposited, the laser scanning steps of each continuous layer are duplicated to form a thick substrate until the desired object is obtained. For the production of 3D structures, the substrate is actively adjusted by modifying the reactive gas during the laminating process. The article is formed layer by layer until completed. In the present invention, there is no particular limitation on the particle shape of the base material used in one embodiment. For powders, the average grain size in one embodiment is about 10-100 μm. The properties of metal powders or metal products are improved by chemical reactions that are spatiotemporally (chamber / wire / container, continuous / circulating / multiple steps) controlled during the additional manufacturing process during the manufacturing process.

In certain embodiments, the present invention provides high purity for metal products, except for high dimensional accuracy and good microstructural properties. The metal product has improved substrate phase, crystal structure, and metallurgy structure, and is free from microstructure defects such as gaps, impurities, inclusions, and special microcracks and porosity, and is not metal stamping. In the context of use, the product is considered to be sintered resistant, even though it may be made of pure metal and / or alloy powder materials. The present invention also provides a methodology for adjusting magnetic properties and residual stresses in manufactured products.

The additive manufacturing process according to the present invention is realized in an inert gas environment and is stored in or reacts with the reactive fluid before the substrate enters the build chamber. In such an example, the inert gas environment includes a gas selected from the group consisting of helium, argon, hydrogen, oxygen, nitrogen, air, nitrogen oxides, ammonia, carbon dioxide, and combinations thereof. In one embodiment, the inert gas environment comprises a gas selected from the group consisting of nitrogen (N2), argon (Ar), helium (He), and mixtures thereof. In one embodiment, the inert gas environment is substantially an argon gas environment. Further, the addition manufacturing process according to the present invention is realized in a gas environment of the required reactive fluid, and is stored in the reactive fluid or reacts with the reactive fluid before the base material enters the build chamber.

FIG. 1 is a schematic view of an additional manufacturing apparatus 10 according to an embodiment of the present invention. As shown in FIG. 1, the additional manufacturing apparatus 10 includes a build chamber 100 having a movable manufacturing platform (not shown), on which the object 90 is manufactured. The additional manufacturing apparatus 10 further includes an energy generation system 50 and a controller 40. In an embodiment, the reactive fluid 60 or a plurality of reactive fluids 60', 60'' are brought into contact with the substrate 70 as it is introduced into the build chamber 100 of the addition manufacturing apparatus 10 and generated by the energy generation system 50. Energy is used to create the object 90. When the reactive fluid 60 comes into contact with the base material 70, the surface of the base material becomes the base material 75 (not shown) adjusted and adjusted according to the required result. The adjustment of the surface of the substrate 70 may be the result of chemical adjustment, coating and / or adsorption of the reactive fluid 60. If necessary, the inert gas 80 is introduced into the additional manufacturing apparatus. The object 90 has many types. The controller 40 transmits the control signal 42 to the generation system 50 and the control signal 44 to the build chamber 100 to control the heating of the adjusted base material 75 and the melting in some embodiments to form the object 90. Let me. These control signals 42, 44 can be generated using the data file 30.

The value set by the operator is fed by the computer to set the amount and type of the reactive gas to be brought into contact with the base material 70. This allows the operator to design a chemical profile of each layer within the object 90 during the manufacturing process. This establishes different supply and repeat conditions for at least one reactive gas (60, 60'and / or 60'') to be introduced based on the depositing multi-layer deposition procedure or deposition progression. Be changed.

The description of the additional manufacturing apparatus 10 of FIG. 1 does not imply physical and / or structural limitations that should be different depending on the different environments in which it is performed. For example, in other embodiments, the reactive gas is brought into contact with the substrate at different times, as shown in FIGS. 2 and 3. For example, in one embodiment shown in FIG. 2, the reactive fluid 260 and the substrate 270 are brought into contact with each other at supply line 272, which provides a longer time for the chemical reaction that occurs on the surface of the substrate 270. Will be done. It is also beneficial that the mixture of substrate and reactive gas 260 is exposed in the heating step, thus causing the supply line 272 to consume an external energy source before being introduced into the build chamber (not shown). Further, as described above, the adjusted substrate (not shown) is subsequently introduced into the build chamber 200, in which the object 290 is manufactured. Other embodiments, as shown in FIG. 3, show not only the benefits of adjusting the chemical properties of the substrate surface, but also by storing and transporting the substrate in a reactive fluid 370. It is also shown to achieve improved safety, operability, and transportability of some substrates. For example, microparticles or hypoxic powders are explosive and are suspended in the reactive fluid 370, which greatly enhances the operability and safety of these materials. Table 1 below provides multiple examples of reactive fluids and locations that react with metallic materials during the addition manufacturing process.

The additional manufacturing apparatus 10 shown in FIG. 1 is constructed by adjusting a conventional laser sintering or melting system. In different embodiments, reactive gases are used to replace the inert gases in these systems.

One of the biggest challenges in using powdered materials and manufacturing components by conventional laser addition manufacturing processes is the high reactivity of the powdered material surface with air and / or oxygen. Therefore, residual stresses and defects occur during the manufacturing period of the member. As mentioned above, the contact of the reactive fluid with the metal powder reduces the amount of residual stress due to impurities, crevices, or inclusions, which results in high purity metals, components, or products. It is believed that. In addition, the operator of the additive manufacturing equipment can adjust the mechanical / chemical properties of each layer by using a reactive fluid, which includes the surface of the object to be manufactured, thereby providing geometric flexibility. And process stability is provided separately. It should be noted that the effectiveness of the materials used is increased, for example, recovery, reduction of waste, improvement of safety, operability, and improvement of transportability of oxidized powder are achieved.

As mentioned above, the apparatus 10 is capable of processing a wide variety of materials and includes, but is not limited to, those described below.

Aluminum and its alloys. The base material 70 is pure aluminum or an aluminum alloy. The base material 70 may be a mixture of pure aluminum and particles of at least one aluminum alloy, or a mixture of many kinds of aluminum alloys. There are no restrictions on the composition of the aluminum substrate 70, but an aluminum coating film must be formed on the body with aluminum that contains a sufficient metallic form for the particles of the powder material.

The base material 70 may be nickel and a nickel alloy (including a nickel-based superalloy), or copper and a copper alloy. The substrate 70 may be a refractory metal and includes noble and semi-metals and / or materials with high oxidizing capacity, such as copper, iron, titanium, ruthenium, cadmium, zinc, rhodium, potassium, sodium, nickel, bismuth, etc. Tin, barium, germanium, lithium, strontium, magnesium, beryllium, lead, calcium, molybdenum, tungsten, cobalt, indium, silicon, gallium, iron, zirconium, chromium, boron, manganese, aluminum, lantern, neodymium, niobium, vanadium, Includes yttrium and / or scandium.

The base material 70 may be a metallic glass or a non-crystalline metal compound, a ternary, quaternary, or higher order metal alloy having a non-crystalline structure, for example, aluminum titanium such as Ti-Al-Fe and Ti-Al-N. Base alloys, zirconium base alloys such as Zr-Cu-Al-Ni, palladium base alloys such as Pd-Ni-P, iron, boron, silicon, carbon, phosphorus, nickel, cobalt, chromium, nitrogen, titanium, zirconium, vanadium It may be an iron-based alloy containing a combination of, and niobium. In the production of these metallic glasses, boron, phosphorus, silicon, carbon, and / or any element is used in a reactive fluid such as diborane, hydrogen phosphate, methane and added into the apparatus 10. The present invention is applied to form amorphous metal oxides such as In-Ga-Zn-O and Zn-Rh-O. A reactive fluid such as oxygen or hydrogen peroxide is used as the oxide to be formed in the apparatus 10.

Many types of reactive fluids are selected for the present invention. For example, reducing agents such as hydrogen, carbon monoxide, formic acid, ammonia, hydrazine, monomethylhydrazine, 1,2-dimethylhydrazine, methane, ethane, propane, butane, pentane, hexane, heptane, and higher order hydrocarbon compounds. Saturated hydrocarbon compounds such as acetylene, propylene, butene isomers, and carbonizing agents / carving agents such as unsaturated hydrocarbon compounds such as ethylene, carbon dioxide, oxygen, carbon tetrafluoride, fluoroformun, etc. Oxidants such as methylenedifluoride, fluoromethane, hydrogen peroxide, ozone, nitrogen peroxide, nitrogen monoxide, nitrogen dioxide, nitrogen trifluoride, fluorine, monomethylamine, dimethylamine, trimethylamine, ammonia, hydrazine, monomethylhydrazine, Nitrides such as 1,2-dimethylhydrazine, boring agents such as diborane, trimethylboron, tetramethyldiborane, boron trichloride, boron trifluoride, hydrogen sulfide, methanethiol, ethanethiol, propanethiol, butanethiol, pentane. Sulfurizing agents such as thiol and dialkyl sulfide, hydrogen phosphide, tert-butylphosphine, triethylphosphine, trimethylphosphine, phosphoryl chloride, trifluorophosphine, phosphorinating agents such as trichlorophosphine, monosilane, disilane, higher silane, alkylsilane, Silane agents such as tetraethoxysilane, fluorosilane, chlorosilane, aminosilane, selenium agents such as hydrogen selenium, alkylselenide, plasma and supercritical fluids, tungsten hexafluoride, trimethylaluminum, tetraethylaluminum, trimethylgallium, tetraethyl. Other reactive fluids such as gallium, tetrachlorotitanium, transition metal compounds, tungstate agents, and combinations thereof.

Unless otherwise defined, all technical and scientific nouns used herein have meanings familiar to conventional engineers in the technical field to which the present invention belongs. Many methods and materials similar to or equivalent to those described for the present invention are used in the practice of the present invention, provided that materials and methods according to some embodiments are described herein. Although some embodiments of the present invention will be articulated, many modifications and modifications thereof can be made by conventional technicians. It is considered that a conventional engineer can make maximum use of the present invention according to the description of the present invention without further explanation.

By describing some embodiments, it is possible for conventional engineers to use various adjustments, alternative structures, and equivalents without departing from the spirit of the embodiments of the present invention. .. Also, many conventional processes and components are not described herein to avoid unnecessary confusion about the present invention. Therefore, the above description does not limit the scope of the present invention.

When a range of numbers is provided, each intervening value between the upper and lower limits of the range (unless otherwise explicitly stated in the preceding and following sentences, the lower limit, unless otherwise specified in the preceding and following sentences). It should be understood that (up to one tenth of the unit) is also specifically stated. Also included are intervening values within each small range or stated range between all the stated values and any other stated numerical value or intervening value within the stated range. The upper and lower limits of these small ranges are included or excluded independently within the above range, and each range is also included in the present invention, and one, two, or zero limit values thereof are within the small range. And limited by specially excluded limits within the range described above. If the stated range contains one or two limits, it also includes a range in which one or two of these included limits are excluded.

Unless otherwise specified in the preceding and following sentences, "one" or "above" described in the present invention and the scope of patent application includes a plurality of referents. Thus, for example, "one process" includes a plurality of such processes, and "dielectric material" includes one or more dielectric materials and equivalents familiar to conventional engineers.

Also, as used in the present invention, "including" or "providing" is a description of the existence of the described feature, whole, member, or process, provided that one or more other features, whole, member, etc. It does not prohibit the addition of processes, actions or groups.

10 Additional manufacturing equipment 210 Additional manufacturing equipment 310 Additional manufacturing equipment 30 Data file 230 Data file 330 Data file 40 Controller 240 Controller 340 Controller 42 Control signal 44 Control signal 50 Energy generation system 250 Energy generation system 350 Energy generation system 60 Reactive fluid 60 'Reactive fluid 60'' Reactive fluid 260 Reactive fluid 260' Reactive fluid 260'' Reactive fluid 70 Base material 270 Base material 80 Inactive gas 280 Inactive gas 380 Inactive gas 90 Object 290 Object 390 Object 100 Build chamber 200 Build chamber 300 Build chamber 272 Supply line 370 Reactive fluid / base material 370'Reactive fluid / base material 370'' Reactive fluid / base material

Claims (28)

An additional manufacturing method that manufactures an object on a manufacturing platform.
The one or more reactive fluid (i) at least one having at least one surface which is adjusted to the chemical resistance required by the reactive fluid substrate及beauty (ii) said one or more first the first quantity of at least one substrate for the reaction fluid having a contaminated surface impurities are deposited manufacturing platform, production platform, a step disposed in the build chamber,
By introducing one or more of the first reactive fluids into the build chamber, the surface of the substrate is adjusted to the required chemical properties and has an impurity-free, chemically adjusted surface. A step in which a conditioned reactive substrate is produced and energy is applied to the entire at least one substrate to form a first layer or substrate.
A step of depositing a second quantity of the at least one substrate to form at least another layer on the substrate and introducing one or more other reactive fluids into the build chamber.
The one or more other reactive fluids
(I) is identical to the one or more reactive fluid, Ri and (ii) the one or more reactive der the substrate having a surface which is adjusted to the chemical resistance required by the reaction fluid ,
(Iii) a non-reactive impurities located on the one or more of the at least one surface of the substrate that have a surface which is adjusted to the chemical resistance required by the reaction fluid, or,
(Iv) the one or more least reactive flow body one that is reactive to a substrate having a surface which is adjusted to the chemical resistance required by the one or more reactive fluid or more other reaction Unlike sexual fluids, it is reactive with at least one substrate having the surface contaminated with impurities and is also reactive with the impurities.
By applying energy to the entire first layer or at least the other layer deposited on the substrate, the at least the other layer is melted in the first layer or the substrate.
The other quantity of the at least one substrate is continuously formed on the layer formed in advance until the production of the object is completed, and the one or more other reactive fluids are added to the build. An additional manufacturing method comprising a step of being introduced into a chamber and applying energy to the entire formed layer. The addition production according to claim 1, wherein the additive production is selected from the group composed of hydrogen as an impurity on the surface of the at least one substrate which is reactive with the one or a plurality of other reactive fluids. Law. The adjusted reactive substrate reduces the drawbacks of at least one microstructure of the first layer and at least the other layer of the substrate, and the drawbacks of the at least one microstructure include impurities, microcracks and porosity. The additional manufacturing method according to claim 1, wherein the method is selected from a group composed of. The addition according to claim 1, wherein the adjusted surface of the at least one adjusted reactive substrate improves one of the phase, crystal structure, and metallurgical structure of the substrate. Manufacturing method. The addition manufacturing method according to claim 1, wherein the magnetism of the object produced by the adjusted surface of the at least one adjusted reactive substrate is adjusted. The addition manufacturing method according to claim 1, wherein the prepared surface of the at least one adjusted reactive substrate adjusts the residual stress property of the object to be manufactured. The addition manufacturing method according to claim 1, wherein the at least one reactive base material is selected from a group composed of a powder material, plasma, a prism, a wire, or a fluid. The addition manufacturing method according to claim 7, wherein the powder material is a metal powder material. The addition manufacturing method according to claim 8, wherein the metal powder material is a metallic glass material or an amorphous metal compound material. The metal powder material is selected from a group composed of aluminum, nickel, iron, titanium, copper, fire-resistant metals, and alloys thereof, and is easily oxidized, and the oxidation reacts with air and / or oxygen and the surface. The additional manufacturing method according to claim 8, wherein the metal is generated by the above-mentioned method. The addition manufacturing method according to claim 8, wherein the metal powder material easily absorbs moisture. The addition manufacturing method according to claim 1, wherein the at least one other reactive fluid is selected from a group composed of gas, plasma, supercritical fluid, and a combination thereof. As the at least one reactive fluid, a reducing agent, a carbonizing agent, an oxidizing agent, a nitriding agent, a boring agent, a sulfurizing agent, a phosphoring agent, a silicifying agent, a selenium agent, a tungstenizing agent, and a carbonizing agent ( The addition manufacturing method according to claim 12, wherein the carbonizer agents ) and a group composed of a combination thereof are selected. The addition manufacturing method according to claim 1, further comprising a step of forming a new surface on the object manufactured by laser cutting and exposing the new surface to the at least one reactive fluid. The addition manufacturing method according to claim 1, wherein the applied energy is electron beam processing. The addition manufacturing method according to claim 12 , wherein any or all of the new surface portions can be adjusted to the chemistry required by the reactive fluid. The addition manufacturing method according to claim 1, wherein the surface that can be adjusted to the required chemistry is applied by the reactive fluid. The addition manufacturing method according to claim 1, wherein the surface that can be adjusted to the required chemistry is formed by absorption of the reactive fluid. An additional manufacturing method that manufactures an object on a manufacturing platform.
Prior to the entry of at least one conditioned substrate into the build chamber, the at least one conditioned substrate having the required chemistry is formed and the one or more reactive fluids are said one or more. Reactive with at least one substrate having a chemically adjustable surface required by the reactive fluid.
The step of introducing the at least one adjusted substrate into the build chamber having the manufacturing platform.
A first quantity of said at least one adjusted substrate is applied to the manufacturing platform and energy is applied to the first quantity of said at least one adjusted substrate to apply the energy to the at least one adjusted substrate. The process of melting multiple particles of material into the first layer or substrate,
Energy is applied to at least one second quantity of the at least one adjusted substrate deposited on the substrate, and the particles of the second quantity of the at least one adjusted substrate are melted into the substrate. And at least another layer is formed on the substrate.
An additional manufacturing method comprising a step of continuously forming each layer of a base material to be adjusted on the substrate until the manufacturing of the target body is completed. The adjusted surface of the one or more substrates reduces the defects of at least one microstructure of the first layer and at least the other layer, and the drawbacks of the at least one microstructure include impurities, microcracks, etc. The addition manufacturing method according to claim 19, wherein the method is selected from the group composed of the porous material and the porous material. The addition manufacturing method according to claim 19, wherein the adjusted surface of the at least one adjusted substrate improves one of the phase, crystal structure, and metallurgical structure of the substrate. .. The additional manufacturing method according to claim 19, wherein the magnetism of the manufacturing object is adjusted by the adjusted surface of the at least one adjusted base material. The addition manufacturing method according to claim 19, wherein the residual stress property of the manufacturing object is adjusted by the adjusted surface of the at least one adjusted base material. An additional manufacturing method that manufactures an object with enhanced mechanical strength on a manufacturing platform.
At least one reactive base material is stored in the gas that removes hydrogen, a base material that does not contain hydrogen is formed, and the gas that removes hydrogen is _{composed of CO, CO 2} , a fluorocarbon compound, or a mixture thereof. Processes selected from the group and
The process of introducing the hydrogen-free substrate into a build chamber having a manufacturing platform, and
The first quantity of the hydrogen-free substrate is applied to the manufacturing platform, and energy is applied to the first quantity of the hydrogen-free substrate, so that the first quantity of the hydrogen-free substrate is applied. An additional manufacturing method comprising a step of melting as a first layer or a substrate. The addition manufacturing method according to claim 24 , wherein the applied energy is thermal diffusion. A step in which energy is applied to at least one second quantity of substrate deposited on the substrate, the second quantity of the substrate is melted into the substrate, and at least another layer is formed on the substrate. When,
The additional manufacturing method according to claim 24 , wherein each layer of the base material is continuously formed on the substrate until the manufacturing of the target body is completed. Claims, characterized in that it is selected from the first layer and the at least other impurities as more of at least one of the disadvantages of the microstructure, the group consisting of microcracks, and porosity by substrate not including the hydrogen 26. The additional manufacturing method. The addition manufacturing method according to claim 26 , wherein the residual stress property of the manufactured object is adjusted by the hydrogen-free base material.

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